Allyl and methallyl esters of lactic and alpha-acetoxypropionic acids



lactate. crotyl Patented Nov. s, 1946' FECE,

mm, m warmer. names or mono m mna-Aca'roxrrnorromo aoms Che a. Rehberg, Glenside, and Charles H.- Fisher, Abington, Pm, assignors to United States of America, as represented by the Secreof Agriculture No Drawing. Application December 8, 1944, Serial No. 567,294

4 Claims.

(Granted under the-act of March 3, 1883, as

' the Government of the United States of America for governmental purposes without the payment to us of any royalty thereon.

This is a continuation in part of our copending application for patent, Serial No. 474,757, filed February 4, 1943.

Our invention relates tonew and useful allyl and substituted allyl esters of lactic and alphaacetoxypropionic acids, namely, allyl lactate, beta-methallyl lactate (hereinafter referred to as methallyl lactate), beta-chloroallyl lactate, gamma-chloroallyl lactate, methyl vinyl carbinyl lactate, ally! alpha-acetoxypropionate. beta-methallyl alpha-acetoxyproplonate (hereinafter referred to as methallyl alpha acetoxypropionate"), beta -chl0roa1lyl ,alpha acetoxypropionate, gamma chloroallyl alpha-acetoxypropionate, methyl vinyl carbinyl alpha acetoxypropionate, and crotyl alphaaceto ropionate, having the formulae:

CHaCHOHCOOCHzCHICH: allyl lactate v CHJCHOHCOOGEC (CH1) :CH: methallyl lactate CHJCHOHCOOH:C(CD :CH: beta-chloroallyl lactate cmcnoncoocmcnzcncl gamma-chloroallyl lactate CH3CHOHCOOCH(CK1) CH :CH: methyl vinyl carbinyl lactate CI'IJCHOHCOOCHZCHZCHCHJ crotyl lactate crncoocmcmicoocrncnzcm ally] alpha-acetoxypropionate cmcoocmcrm COOC'HzCKZfi) :CH: methaliyl alpha-acetoxypropionate cnscoocmcmwoocmcwn :cm beta-chloroallyl alpha-acetoxypropionate cmcoocmcmicoocmcmcnci gamma-chloroallyl alpha-acetoxypropionate CH:COOCH(CHJ)CQOCH(CHJ) CH:CH: methyl vinyl carbinyl alpha-acetoxypropionate CHsCOOCH(Hs) COOCH2CH:CHCH3 crotyl alpha-acetoxypropionate amendedAp'ril 30, 1928: 370 0. G. 757),

of compounds that are usefulv as solvents, plasticizers, insecticides, insect repellants, chemical intermediates and as starting materials in the production of allyl and substituted allyl acrylates which are substances polymerizable into plastic,

semi-solid, or solid materials useful in industry because of their tensile strength, elasticity. plasticity, resistance to water, organic liquids and gases, and because of other desirable properties.

It is well l-rnown (Burns, Jones and Ritchie, J. Chem. Soc. 1935, 400-6, 714-7; Claborn, U. S. 2,222,363, Nov. 19, 1940; Claborn, U. S. 2,229,997, Jan. 28, 1941; Smith, Fisher, Ratchford and Fein, Ind. Eng. Chem. 34, 473-9 (1942)) that methyl alpha-acetoxypropionate can be decomposed thermally to yield as a principal product methyl acrylate, which can be converted by polymerize tion into substances useful in theplastlcs andrelated industries. However, the alkyl alphaacetoxyproplonates of higher molecular weight have been observed to .be unsuitable for production of the corresponding alkyl acrylates because of the preponderance of undesirable reactions which lead to the formation of products other than the a'crylates, and because the alkyl acrylates formed yield polymers which lack the properties considered desirable in industry.

We have found that the presence of an olefin linkage between the beta and gamma carbon atoms of the alkoxy group decreases the undesir-v able side reactions encountered in the pyrolysis of the alkyl alpha-acetoxypropionates of higher molecular weight, and that, owing to the characteristics of the ally] and substituted allyl radii cals and their, esters, their alpha-acetoxypropionates can be converted readily and in good yields into allyl and substituted allyl acrylates (as shown below), which can be polymerized and interpolymerized into materials useful in industry.

Pyrolysis cmcoocmcm)coocmtcmycmn Ally] or substituted allyl alpha-acetoxypropionatc CH;:CIICOOC(R);C(R):C(li): (where R is hydrogen, a

halogen or an. alkyl group) Ailyl or substituted allyl acryiair- Thus we have found that allyl, methallyl, chloroallyl (of the beta and gamma variety), methyl vinyl carbinyl, and crotyl lactates, and allyl, methallyl, chloroallyl (oi the beta and gamma variety).

The object of our invention is the production 56 and polymers interpol mers thereof;

Allyl lactate can be made by the interaction of lactic acid and aliyl alcohol or by treating metallic salts of lactic acid with an aliyl halide. Methaliyl lactate can be made from lactic acid and methallyl alcohol by esterification, from an alkyl lactate, such as methyl or ethyl lactate and methallyl alcohol by aicoholysis, or from a metal lactate, such as sodium actate, and a beta-methaliyl halide. Methyl vinyl carbinyl, beta-chloroallyl. and crotyl lactates are prepared bythe interaction of lactic acid and the respective alcohols, while gamma-chloroallyl lactate can be conyeniently prepared by the action oi gammachloroallyl alcohol or methyl lactate.

Allyl and methallyl alpha-acetoxypropionates can be prepared from allyl and methallyl lactates, respectively, by acetylation with any of the common acetylating agents, such as acetic anhydride. They can also be prepared by treating aipha-acetoxypropionyl chloride or alpha-acetoxypropionic anhydride with ally] and methaliyl alcohol, respectively. Beta-chloroallyl, gammachloroallyl, methyl vinyl carbinyl, and crotyi alpha-acetoxypropionates can'be conveniently prepared by treating the corresponding iactates with an acetylating agent such as acetic anhydride.

The ,iollowing are several examples or the invention:

Example I.--Two moles (180.2 g.) of essentially 100 percent lactic acid, 2.2 moles (127.8 g.) oi allyl alcohol, 200 cc. of benzene and 3 cc. of concentrated sulfuric acid were refluxed three hours while water was continuously removed as formed by use of a trap. Benzene and unreacted ailyl alcohol were removed by distillation under about 20 mm. pressure, after which allyl lactate was distilled under 1 mm. pressure, its boiling point under this pressure being 27-29" C. The yield was 88 g., or 34 percent or the theoretical. More or the ester, allyl lactate, was obtained by adding allyl alcohol, benzene and acid catalyst to the distillation residue r'efluxing and then distilling the reaction mixture as before. Example II.-Two moles (180.2 g.) of essentialiy 100 percent lactic acid was dehydrated by refluxing with benzene, a trap being used to remove water. After complete removal or water (34 cc.), 6 moles of allyl alcohol was added and the mixture was refluxed several hours. The benzene and excess alcohol were then removed by vfractional distillation, the final stage being carried out under a pressure oi. about 20 mm. The allyl lactate was then distilled at 60 C. under 7 mm. pressure, 45 g. being obtained. The recovered alcohol was returned to the reaction vessel containing the distillation residue, 1-2 g. of p-toluenesullonic acid was added. and the mixture again refluxed for several hours. Upon distillation, 159 g. of allyl lactate was obtained. The total yield was thus 204 g., or 78 percent of the theoretical. The residue (presumably polylactlc acid) could doubtless be used again or added to a new batch of material, thus eventually converting virtually all of it into ester.

Allyl lactate is a clear, colorless, mobile liquid at room temperature with a mild and not unpleasant odor; boiling at 60 C. under 7 mm. of mercury pressure, 79 C. under 25 mm., and 175.5 C, under 754 mm. pressure: having a speciflc gravity 01 1.0452 at 20 C.. and having a refractive index or the yellow sodium line of 1.4369 at Example [IL-Using essentially the same procedure as in Example I. there was obtained from 3 moles (27 g.) of lactic acid and 3.3 mole g.) of beta-methallyl alcohol 143 g. of ester, this being 33 percent or the theoretical amount. As before, more 0! the ester was obtained by treating the distillation residue with beta-meth- 5 ylaliyl alcohol, refluxing and distilling.

Example IV.-Five moles (450 g.) of lactic acid and 5.5 moles (396 g.) of beta-methallyl alcohol were treated as in Example I, the yield of ester being 212 g. The recovered alcohol was then returned to the reaction flask containing the;

product was collected at 77-79 C. under 11 mm.

pressure.

Beta-methallyl lactate is a clear, colorless,

mobile liquid at room temperature, with mild g5 odor; having boiling points of 69 C. under 8 mm. and 78 C. under 11 mm. of pressure; having a speciflc gravity of 1.0181 at C., and having a refractive index for the yellow sodium line of 1.4389 at 20 C.

Example V.To 1.5 moles (195 g.) of allyl lactate there was slowly added, with stirring, 1.85

moles (168 g.), 10 percent excess, of acetic anhydride. The mixture was warmed to 50-60" C.

to start the reaction, after which cooling was 85 used to keep the temperature below 100-110 C.

Alter standing an hour, the mixture was iractionated under a pressure or 7 mm., the product being collected at 80-81 C. The yield was 230 g., or 89 percent of the theoretical.

co Ailyl alpha-acetoxypropionate is a clear, colorless, mobile liquid of slight, though pleasant. odor; having a boiling point of 81 C. under 7 mm.; having a specific gravity of 1.0544 at 20 C.: and having a refractive index for the yellow sodium line of 1.4270 at 20 0.

Example VI.--Using essentially the procedure described in Example V. except that 1-2 cc. phosphoric acid was used as a catalyst and the temperature was maintained at 60-80 0.. there was obtained from 1.5 moles of beta-methallyl lactate and 1.8 moles of acetic anhydride 8. yield of 260 g. of beta-methallyl alpha-acetoxypropionate, this being 93 percent of the theoretical yield. The product was collected at 100-102 C.

at 12 mm. pressure.

Beta-methallyl alpha-acetomropionate is a clear, colorless, mobile liquid with a slight, pleasant odor: having boiling points of 76 C. under 3 mm., 87 C. under 5 mm., and 95 C. under 10 mm. pressure; having a specific gravity of 1.0330

at 20 C., and having a refractive index for the yellow sodium line of 1.4314 at 20 C.

Example Vile-Aqueous sodium lactat (84.5

g. of 64 percent by weight sodium lactate) and 55 67.8 g. of beta-methallyl chloride were heated in a rocking stainless steel autoclave at 120-180 C. for 5 hours. A moderate yield of methallyl lactate was obtained by fractional distillation of the reaction mixture.

Example VIII.Ten moles (1125 a.) o! Percent lactic acid, 400 ml. benzene. and 5 ml. of suluric acid were refluxed in a still having a 841;. column fitted with a water trap at its top, water being drawn ed, as it collected. at the rate of 7 about 300 ml. in about 5 hours. when production of water became slow, 40 moles (2323's.) of allyl alcohol were added and refluxin! continued with removal of about 220 cc. of water, containing some allyl alcohol, in about 20 hours. When no more water was produced, the flask was cooled, 20 g. of anhydrous sodium acetate was added to neutralize the sulfuric acid, and the benzene and about half the excess allyl alcohol were'dlstilled at atmospheric pressure. The remainder of the alcohol was then distilled fairly rapidly under about 50 mm. pressure, after which the allyl lactate was rapidly distilled at 60 C. and at '7 mm. The yield was 1178 g. or 90.5 percent of the theoretical.

Example IX.Using the procedure described in Example VIII, lactic acid was interacted with beta-chloroallyl alcohol to give beta-chloroallyl lactate in '76 percent yield.

Example X.The procedure of Example 'V'IH was slightly modified to prepare methyl vinyl carbinyl lactate, since methyl vinyl carblnol is somewhat unstable in the presence of sulfuric acid. In this case, the lactic acid, alcohol, and benzene were mixed and refluxed with removal oi. water until little water was produced. Then, g. of p-toluenesulionic' acid was added and heating continued. When no more water was proat the still-head. when production of methanol ceased, the excess alcohol was distilled at 54 C. and at 13 mm., after which the product was obtainedat 105 C. and at 12 mm. The yield of gamma-chloroallyl lactate was 65 percent of the theoretical.

Example XML-Using the procedure of Example XII, methallyl lactate was obtained by interacting methyl or ethyl lactate with methallyl alcohol. The yield of methallyi lactate was '70 percent.

Example XIV. Beta-chloroallyl alpha-acetoxypropionate was prepared by interacting betachloroallyl lactate with acetic 'anhydride and then distilling to recover the ester.

Example XV.Gamma-chloroal lyl alpha-acetoxypropionate was prepared by reacting gammachloroallyl lactate and acetic anhydride.

Example XVI.Methyl vinyl carbinyl alphaacetoxypropionate was prepared by reacting methyl vinyl "carbinyl lactate and acetic anhydride.

Example XVII. Crotyl alpha-acetoxypropionate wa'sprepared by reacting crotyl lactate with acetic anhydride.

The following table illustrates the properties of some of these compounds:

Monoand (ii-esters of lactic acid Yin] B Moi. refraction Bap. eq. EM and. 5." ill r Oalcd. Found Calod. Found ALKENYL LAC'IATES Beta-chloroallyl 76 7 83 5 1. 4627 1. 2158 37. 49 87. 23 164. 6 163. 2 Gammn-ohloroallyl 6b 106 12 1. 4070 1. 2168 37. 49 87. 54 1M. 0 Crotyl 83 92 18 1. M20 1. 0108 87. 24 37. 75 144. 2 149. 8 Methyl vinyl carbinyl 77 58 8 1. 4328 1. 0091 37. 24 37. 10 144. 2 144. 5

ALKENYL ALPHA-ACETOXY?BOPIONATES Beta-chlorodllyl 34 96 5 1. 44.80 1. 1792 46. 86 40. 7B 103. 3 102. 0 Crotyl 86 9'1 8 1.4347 1.0838 46.60 46.97 93.1 95.1 Methyl vinyl earbinyl .1 100 80 8 1. 4255 l. 0233 46. 00 d0. 59 93. 1 9a 2 l Prepared by treating the corresponding aikenyl lactate with acetic anhydride.

Having thus described our invention, we claim: 1. Beta-chloroallyl alpha-acetoxypropionate. 2. Gamma chloroallyl alpha acetcxypropionate.

3. Methyl 'vinyl carbinyl alpha-acetoxypropionate 4. A compound of the general formula where (X) is a substituted allyl radical chosen. 

